In the photographic processing of silver halide light-sensitive materials, an important object has been to provide a satisfactory photographic image in a stable manner. This object has become more difficult to accomplish particularly in view of the latest requirements for speeding up of processing and reducing the rate of replenishment so that the amount of waste liquid can be reduced. For obtaining a satisfactory photographic image in a stable manner, the most significant factor is for photographic processing solutions to be stable against deterioration with the passage of time, such as by air oxidation. In particular, in the current color photographic processing systems where reduction of washing water or stabilizing processing has become widespread, improvement in the stability of the bleach-fixing or fixing bath and the subsequent washing or stabilizing bath is of extreme importance.
Carbonyl-bisulfite addition compounds have hitherto been proposed as a preservative and as a means for improving the stability of a bleach-fixing or fixing bath. For example, methods of using these carbonyl-bisulfite addition compounds as a preservative for a bleach-fixing or fixing bath are described in JP-A-48-42733 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-50-51326, JP-A-56-107244, and West German Patent 2,102,713. However, although carbonyl-bisulfite addition compounds exhibit excellent performance as a preservative for a bleach-fixing or fixing bath, they have not yet been practically used because various problems arise in their use. In particular, when a conventional photographic light-sensitive material is processed with a bleach-fixing bath containing a carbonyl-bisulfite addition compound as a preservative, the resulting image has deteriorated preservability. That is, when the processed light-sensitive material is stored, the minimum density on the undeveloped area (D.sub.min) increases with the passage of time and stain is generated. Moreover, lower aliphatic aldehydes, of the available carbonyl compounds, have a low vapor pressure and therefore give rise to handling problems and environmental problems, such as odor. Hence, there has been a strong desire for a method of processing a silver halide color photographic material in which a bleach-fixing or fixing bath exhibits excellent stability without causing deterioration of the resulting image with the passage of time or any other problems occurring.
On the other hand, it is known to add a specific sulfinic acid to a processing solution as disclosed, for example, in JP-B-49-33787 (the term "JP-B" as used herein means an "examined Japanese patent publication"), British Patent 571,078, and U.S. Pat. No. 3,293,036. JP-B-49-33787 relates to black-and-white development, and British Patent 571,078 relates to silver dye bleaching, both differing from the present invention in object of using a sulfinic acid and containing no disclosure at all as to stain prevention of color light-sensitive materials. Further, the compounds disclosed in U.S. Pat. No. 3,293,036 have been found not to produce any effect on image stain generated with the passage of time. Although British Patent 1,379,615 states that the sulfinic acid can be used to improve the stability of a bleach-fixing bath per se, there is no suggestion as to stain prevention of color light-sensitive materials.
In addition, JP-A-1-230039 describes the use of a sulfinic acid for stabilizing a processing solution and for prevention of stain of color light-sensitive materials. However, the effects produced are insufficient, or the solubility of the sulfinic acid in a processing solution is insufficient.
It has been proposed to conduct bleaching or bleach-fixing by replacing conventionally employed (ethylenediaminetetraacetato)iron (III) complexes with a bleaching agent having a higher oxidizing power thereby to shorten the processing time or to reduce the amount of waste liquid. That is, use of a powerful oxidizing agent as a bleaching agent is expected to increase the rate of bleaching reaction to thereby achieve rapid bleaching or bleach-fixing. It is also expected that a bleaching bath or a bleach-fixing bath maintains a high bleaching ability even if it is fatigued due to consumption of the oxidizing agent (bleaching agent) and accumulation of silver ion and halogen ion as the processing progresses thereby to decrease the amount of replenisher needed.
It has turned out, however, that such a powerful oxidizing agent (bleaching agent), when employed in a bleaching bath, diminishes the stability of the succeeding fixing bath with the passage of time due to the carry-over, or, when used in a bleach-fixing bath, considerably reduces the stability of the bleach-fixing bath per se with the passage of time, thus retarding the bleach-desilvering reaction. As a result, the succeeding washing or stabilizing bath also has reduced stability with the passage of time. It has thus been demanded to develop a technique for improving stability of a bleach-fixing bath or a fixing bath with time.
It has been proposed in JP-A-1-267540 to improve the stability of processing solutions by addition of a carbonyl-bisulfite addition compound and a compound having an amino group as a functional group to a bleach-fixing bath. However, the inventors have proved that a processing solution containing a carbonyl-bisulfite addition compound and a compound having an amino group forms a precipitate or a color change to black brown occurs on aging.